Polymerization and copolymerization of olefins and resulting products

ABSTRACT

OLEFINS ARE POLYMERIZED AND COPOLYMERIZED BY BEING CONTACTED WITH A CATALYST OF THE FOLLOWING COMPONENTS: (A) A GROUP IV, V OR VI METAL OR A HYDRIDE OR AN ORGANOMETALLIC COMPOUND THEREOF; (B) AN ALKOXY HALIDE OF TITANIUM, ZIRCONIUM OR VANADIUM AND (C) A HALIDE OF A GROUP III OR V ELEMENT. THERE CANTHUS BE OBTAINED POLYOLEFINS WHICH ARE MORE LINEAR AND CRYSTALLINE THAN THOSE OF THE PRIOR ART.

United States Patent 3,573,266 POLYMERIZATION AND COPOLYMERIZATION 0FOLEFINS AND RESULTING PRODUCTS Jacques Stevens, Braine-lAlleud, Belgium,assignor to Solvay et Cie, Societe Anonyme, Brussels, Belgium NoDrawing. Filed July 10, 1967, Ser. No. 651,973 Claims priority,application France, July 19, 1966,

69,897 Int. Cl. C08f 1/56, 3/06 U.S. Cl. 26088.2 6 Claims ABSTRACT OFTHE DISCLOSURE Olefins are polymerized and copolymerized by beingcontacted with a catalyst of the following components: (a) a Group IV, Vor VI metal or a hydride or an organometallic compound thereof; (b) analkoxy halide of titanium, zirconium or vanadium and (c) a halide of aGroup III or V element. There can thus be obtained polyolefins which aremore linear and crystalline than those of the prior art.

BACKGROUND OF THE INVENTION The present invention is directed to aprocess for the polymerization and the copolymerization of olefins andin particular ethylene, in the presence of improved catalysts and to theimproved polymers and copolymers thereby obtained.

In French Pat. No. 1,174,783 of May 3, 1957, it has been proposed topolymerize and to copolymerize olefins in the presence of a ternarycatalyst comprising:

(a) A metal of the IVth, Vth or VIth group of the Periodic Table of theelements or a hydride or an organometallic compound of that metal;

(b) A mineral compound of a polyvalent metal having at least threevalences;

(c) A halide of an element of the IIIrd or the Vth group of the PeriodicTable.

Such a catalytic system is formed, for example, by the reaction of analkyl derivative of lead or tin with titanium tetrachloride, and theaddition of an anhydrous aluminum chloride or boron fluoride.

In these catalytic systems, the mineral compound of the polyvalent metalis usually an inorganic derivative of titanium, zirconium or vanadium.

SUMMARY OF THE INVENTION It has now been found that by modifying thenature of this last-named element of the catalyst, polymerizationproducts having different properties may be obtained. Thus it ispossible to improve the properties of the polyolefins.

This result may be attained by replacing the mineral compound of apolyvalent metal having at least three valences with certain particularorganic compounds of the same metals.

The invention comprises carrying out the polymerization and thecopolymerization of olefins in the presence of a ternary catalystcomprising:

(a) A metal of the IVth, Vth or VIth group of the Periodic Table or ahydride or an organometallic compound of that metal;

(b) A compound of the formula wherein M is titanium, zirconium orvanadium, R is a hydrocarbon radical, X is a halogen, and n and m areeach an integer greater than 0, the sum of n+m being equal to thevalence of M; and

3,573,266 Patented Mar. 30, 1971 (c) A halide of an element of the IIIrdor the Vth group of the Periodic Table.

The invention further comprises the improved polyolefins produced by theprocess of the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Cl Ti( OR) 2 in which R is analkyl group containing 1 to 20 carbon atoms are particularly preferredcompounds for the production according to the invention of catalystshaving advantageous properties. Also preferred are the trialkoxytitanium monochlorides and the monoalkoxy titanium trichlorides.Furthermore similar results may be obtained With compounds in which thechlorine atom is replaced with bromine or another halogen, and the alkylgroups are replaced with aryl, alkylaryl, arylalkyl or cycloalkylgroups. p

The haloalkoxy titanium compounds may easily be obtained either by thereaction between a tetrahalide and a tetraalkoxide of titanium or by thereaction of a hydroxy derivative and a titanium tetrahalide. In the lastcase, the alkoxy halides may be obtained as complexes with the hydroxyderivatives, i.e., a portion of the hydroxy derivative may complex toproduce a complex of the alkoxy halide rather than react with thetitanium tetrahalide to form alkoxy halide. The hydroxy derivative ispreferably an alcohol.

The molecular ratio of the reactants is directly responsible for thestructure of the alkoxy halide which is formed. For example:

In the case wherein a hydroxy derivative is used, it should beremembered for determining the proportion of the reactant, that aportion of the hydroxy derivative could be used up in the formation ofthe aforementioned complexes.

The preparation of the alkoxy titanium halide may be carried out beforepreparing the polymerization catalyst. The alkoxy titanium halide can beprepared in situ in the container where it is intended to prepare thecatalyst and also simultaneously with the preparation of the catalyst.

In this last case, four reactants instead of three are used for thepreparation of the catalyst:

(a) A metal of the IVth, Vth or VIth group of the Periodic Table or ahydride or an organometallic compound of that metal,

(b A titanium, zirconium or vanadium halide,

(b An alkoxy compound of the same metal or a hydroxy derivative ROH, inwhich R is as hereinabove defined,

(c) A halide of an element of the IIIrd or the Vth group of the PeriodicTable.

The order in which the reactants used for the preparation of thecatalyst are introduced is not an essential characteristic of theinvention, though it is preferred to operate as follows in the case whenan alkoxide and a halide are used to form the alkoxy halide:

The M alkoxide is added to the M halide and the reaction of the twocompounds is carried out at a determined temperature, for example from25 to 60 C., for

a period sufficient to have a complete reaction, generally from 30minutes to 2 hours;

Separately, the component a and the component 0, for example tetrabutyltin and aluminum chloride, are reacted;

4 the resulting polyolefins. It has been found that, in most cases, whenall the components of the catalyst are identical, the specific weight ofthe polymer increases when the molar ratio a/ b of the catalystdecreases.

It has also been found that the ratio of the quantities The reactionproduct of this second reaction is added 5 of the components a, b and cwhich are used for the to the M alkoxy halide formed during the firstreaction preparation of the catalyst has an important influence and thetemperature is maint ined at from 20 to 1 C- on its activity. Generally,it is preferred that the molar for 15 minutes to 2 hours to form thepolymerization r ti a/c be from 0,75 to 1.5. catalyst. Another way tomodify the properties of the resulting In the case wherein an alcohol isused instead of an polymers consists in introducing hydrogen into thepoaikOXide the Preparation 0f the aikOXY halide, the merization reactionvessel. The hydrogen acts as a reaction may be carried out under similarconditions, but chain transfer agent, decreases the molecular weight andthe contact period is generally shorter since the reaction therefor inrea es the fusion index of the olyolefins, is more violent. which isoften highly desirable. Hydrogen effects no The catalyst may also beprepared by reacting the marked reduction in the catalytic activity ofthe catalysts alkoxide with a reaction product of the components a f thinvention, and and y gradually adding the M halide- The followingexamples are intended to illustrate the AS another alternative, thecomponents a and b 1 present invention and are not given for the purposeof and 12 may first be reacted and then the component 0 20 limitin thcope thereof, may be added thereto.

Whatever order of reaction is selected, it is preferable, Examples 1 t06 in any case, to carry out these reactions in the absence A series of li ti catalysts r prepared by of solvent. When the reactants are diluted,the reaction i i together, i h absence f l nt, unde an inert Period isextended Without y advantageatmosphere and in the conditions specifiedin Table I y using the Catalysts according to the invention, it isbelow, various titanium alkoxy halides with a certain Possible toProduce Poiyoiefins Which are more linear quantity of the reactionproduct of 14.9 g. tetrabutyl tin and more crystalline than thoseobtained with the cataand 5.74 g. of aluminum chloride. Table Iindicates the lysts of the Prior art and in Particular With thecatalysts quantities of tetrabutyl tin and aluminum chloride useddescribed in French Patent The new eatato make that portion of thereaction product employed lysts are particularly suitable for thepolymerization of in h f h examples, ethylene and its eepeiyinefilationWith other vt-eiefins, in The reaction between the tetrabutyl tin andaluminum particular propylene and butene-lchloride is carried out bymaintaining the two reactants In the ease of Polyethylene, it has beenfound that the in contact with one another in the absence of solvent atProducts Obtained by using the new Catalysts have a true a temperatureof C. for 48 hours. The end of the Specific Weight Which is much higherthan that Obtained reaction is indicated by a complete dissolution ofthe by use of the prior art catalysts. luminu chloride.

The catalystS described in the above identified Freneh The catalysts areintroduced into a 1.5 liter autoclave P for example the Catalysts P pfrom TiCi4, which is kept dry and is flushed with nitrogen, and con-Aicia and 4 9)4, generally Produce polyethylenes 40 tains 700 ml. ofhexane which has been dried on activated having tl'ne Specific Weightsfrom to 0955 alumina. The mixture is heated to C. and ethylene 0n t erhand, the new Catalysts Will Produce p yis introduced therein in such amanner as to maintain a ethylenes having higher specific weights,generally vary- Constant pressure f 15 2 ing from 0957 in 0967 6111-3and in some Cases even After 1 hour gaseous ethylene is removed, theresulthigher- This increase in the true specific Weight, in p c- 5 ingpolyethylene is separated, dried and Weighed, and the tieai terms,corresponds to an increase in the rigidity 4 fusion index and the truespecific weight are determined. of the product and in particular of themolded products The examples R and R given by way of reference, producedtherefrom. Such a rigidity is highly desirable are directed to catalystscomprising a mixture of TiCL, for large molded articles, for examplebottles and other and Ti(OC H which are different from thoseaccordcontainers. ing to the invention.

TABLE I Preparation of the catalyst Polyethylene product Ti(Jln(OR)4-nLength Reaction Fusion True Sn(C4H9)4 A1015 Sn/Tl of the temper-Activity, index, specific Example Weight, Weight, Weight, molar reactionature, Weight, of catag./l0 weight, No. Identity grams grams grams ratioinmin. 0. grams lyst min. g./cm.

R1 TiCl4 0.156 0.745 0.287 2.6 32 -6 49.5 13.3 0.3 0.9487 132.- TKOCQHQA0.755 1. 345 0. 710 1.6 170 30 0 0 1.- TlCl2(OO2H5)z 0.607 1. 845 0.7101.8 63 70 133 4.9 18 0.963 2.- T1Cl2(OC2H5)2 0.651 1. 345 0. 710 1.7 6094.5 3.5 0. 53 0.959 3.. T1C12(OCzH5)2-C2H5OH 0.696 1. 845 0. 710 1.6 8O17 0.62 0.02 0.954 4.-

Tiohto 2115) 0.647 1.345 0. 710 1.6 12 70 187 6.7 4.3 0.955 5TiC1a(OC2H5)-C2H6OH 0.700 1. 845 0. 710 1.9 125 40 3.5 2.7 0.958 6TlOl3(OC2H5)-C2H5OH 0.695 1. 845 0. 710 1.9 25 80 176 6.4 5.3 0.956

1 Grams polyethylene/m.-atmospheres CzHi-g. S11(C4Hn)4.

2 Pressure of ethylene 5 kg/cm.

The increase in the true specific weight of the polyethylenes preparedby using the catalysts according to the present invention is believed tobe due to a higher linearity of the polymer chains. It has been foundthat the polyethylenes obtained according to the process of theinvention have chains containing less than one CH group, from 1 to 1.5vinyl double bonds, from 0.07 to 0.15 vinylidene group and from 0.05 to0.1 trans-internal double bond per 1000 carbon atoms.

The ratio of the quantities of the components a, b and Examples 7 to 17Polymerization catalysts are prepared and tests for the c of thecatalyst has a direct effect on the properties of 75 polymerization ofethylene are carried out exactly under the conditions given in Examples1 to 6, with the excep- The reaction conditions between titaniumtetrachlotion that the alkoxy titanium halide is prepared from ride andthe various alcohols and those used for the preptitanlum tetrachlorideand tetraalkoxy titanium in the aration of the catalyst are given inTable IV, and the vessel in which the catalyst is prepared. resultsconcerning the polyethylene product are given The conditions of thereaction between TiCl and in Table V. Ti(OR) and those for thepreparation of the catalyst are given in Table H, and the properties ofthe resulting polyethylene are given in Table III.

TABLE 11 Preparation of the alkoxyhalide Preparation of catalyst WeightTi(0 R) 4 Temper- Length Tempera of Length of ture of Molar oi the tureof T1014, Weight reaction, reaction, Sn(C4H9)4, AlClz, ratio, reaction,reaction, Example No. grams Identity of R grams min. min. grams gramsSn/Ti min. C

0.25 n-C4H 0.43 1.845 0 710 2.2 60 0.26 n-(hH 0. 43 25 1.845 0 710 2.215 25 0.26 11-0413 0. 43 30 60 1.845 0 710 2.2 30 60 0.24 n-orH, 0.54 3060 1. 845 0 710 1.9 30 60 0.26 l-CBH1 0.38 30 60 1.845 0 710 2.0 30 600.26 i-CsH1 0.38 30 60 1.845 0 710 2.0 30 60 0 31 04H, 0.30 30 60 1.8450 710 1.8 20 80 0 24 04H, 0 38 30 60 1.845 0 710 1.8 145 60 0.22 04H,0.34 30 60 1. 845 0 710 2.0 100 60 0 31 n-CaHir 1.0 30 60 1.845 0 710 1.0 107 70 17 0.26 C4He-CH-CH2- 0 89 30 60 1 845 0 710 1 9 45 70 TABLE IIITABLE V Polyethylene product Polyethylene product True Fusion Truespecif- Fusion specific Rigidity 30 Weight, Activity of index, g./ icweight, Weight, Activity of index, weight, against Example N0. gramscatalyst 1 10 mm. gJcm.

grams eatalyst g./10 min.

36 3 1 a 4 9 1 Grams polyethylene/hr.-a.tmospheres CzHrg. Sn(C4H9)4. 1987. 1 4 11 0 962 2 Partial pressure oi hydrogen:1.5 kgJem.

150 5 As above, 1t 1s found that the catalysts according to1GramsPolyethylene/hratmospheres CzHrg- 511(041104- the inven ion willroduce ol eth lene roducts havin 2 Partial pressure of hydrogen: 10kg./cm. h h ii p h P y y P g 3 Partial pressure of hydrogen: 2 kg./cm. y1g specl c Welg 4 Partial pressure of hy g 1. s Furthermore, Examples 18to 20 show clearly the It is observed that in all cases, when using thecatalysts increase of the true specific weight of the polyethyleneaccording to the invention, it is possible to obtain polyin relation tothe decrease of the molar ratio Sn/Ti. ethylenehaving a true specificweight higher than 0.955 45 and that in some cases, it is possible toattain specific weights at least as high as 0.970 g./cm.

To illustrate the increase of the rigidity of the resulting productswhen using the new catalysts, in Table III there are given resultsobtained according to the ASTM D 747-58T test which should be comparedto the value of 7600 kg./c1n. which characterizes a polyethyleneobtained according to French Pat. No. 1,174,783. g fg fi ExampleCorrespondlng t0 1-845 85- of Examples 18 to 25 I The resulting catalystis introduced into a dry 1.5 Under the same conditions as those given inExamples liter autoclave flushed with nitrogen and containing 700 1 to 6and 7 to 17, polymerization catalysts are prepared ml. of dry hexane.The mixture is heated to 70 C. and

Example 26 A reaction is carried out for a period of 30 minutes at atemperature of C. between 234 mg. of titanium tetrachloride and 344 mg.of Ti(OC H in the absence of solvent and under an inert atmosphere. Theproduct so obtained is mixed with 2.57 g. of the reaction product ofSn(C H and aluminum trichloride prepared as indifrom titaniumtetrachloride, various alcohols, tetrabutyl simultaneously ethylene isintroduced at a constant flow tin and aluminum chloride and tests arecarried out for of 90 g./hr. and propylene at a constant flow of 10 thepolymerization of ethylene. 60 g./ hr.

TABLE IV Preparation of the alkoxyhalide Preparation of the catalyst ROELength I Length Weight of the Reaction Molar or the Reaction ExampleoiTiCh, Identity Weight, reaction, temper- Formula ofresultingSn(C4Ha)4, A1015, ratio reaction, tem er- No. grams 01R grams min.ature,C. product grams grams Sn/T1 min ature, C.

0.39 02115 0.20 15 40 TiC1z(OCzHs)2.C2HaOH 1.845 0.710 2.5 50 60 0.50C2H5 0.245 15 40 TiC12(OCzH5)2.C2H5OH 1.845 0.710 2 60 0.54 C211 0.27 1540 TiC11(OCaH5)2-C2H5OH 1. 845 0.710 1.8 50 60 0.54 0211 0.26 15 40TlC12(OC2Hb)2-C2H5OH 1.845 0.710 1.9 29

0.665 02115 0.26 60 40 TlOl2(OC2Hs)z.CzHsOH 1.845 0.710 1.52 70 0.4751C4H0 0.465 15 40 TlCl2(OlC4H9)2.C4HnOH 1.845 0.710 2.2 60 60 0.5610.119 0.50 15 40 TiGlz(OiC4Hn)2.C4 a 1 84 0.710 1.8 60 80 0.55 C11Hz30.99 15 40 1. 845 0.710 1.8 80 60 After 1 hour, the monomer gases whichhave not reacted are removed and the product is separated, dried andweighed and is examined.

It is observed that 63.5 g. of a copolymer of ethylene and propylene areobtained having a true specific weight of 0.936 g./cm. a fusion index of0.97 and a propylene content, determined by infra-red spectrometry, of36 g./kg. of the resulting product or 2.43 mole percent.

Although specific embodiments of this invention have just beendescribed, it is understood that modifications are permissible withinthe spirit of the invention, the scope of which is to be determined fromthe appended claims only.

What I claim and desire to secure by Letters Patent is:

1. Process for the polymerization of ethylene and the copolymerizationof ethylene with at least one olefin selected from the group consistingof propylene and 1-butene which comprises carrying out saidpolymerization and copolymerization in the presence of a catalystconsisting essentially of:

(a) an alkyl tin,

(b) a compound of the formula Ti(OR) X wherein Ti is titanium, R is ahydrocarbon radical, X is a halogen and n and m are each an integergreater than 0, n+m being equal to 4, and

(c) an aluminum halide, the molar ratio between said alkyl tin and saidaluminum halide being comprised between 0.75 and 1.5.

2. Process according to claim 1, in which the aluminum halide isaluminum chloride.

3. Process according to claim 1- wherein the catalyst is prepared byreacting said alkyl tin and said aluminum halide in the absence ofsolvent, reacting titanium tetralkoxide with titanium tetrahalide in theabsence of solvent at a temperature comprised between about 25 and 60 C.and mixing the products of both reactions at a temperature comprisedbetween about 20 and 100 C.

4. Process according to claim 3 wherein said reaction of said alkoxideof titanium with said halide of titanium and mixing of said products ofboth reactions are carried on in the same vessel.

5. Process according to claim 1 wherein said compound of the formulaTi(OR),,X is a complex of the formula Ti(OR) X -ROH and is prepared byadding a hydroxy derivative of the formula ROH, in which R is as definedin claim 1, to a titanium tetrahalide in the absence of solvent at atemperature comprised between 25 and C.

6. Process according to claim 5 wherein the catalyst is prepared in samevessel as said complex of formula Ti(OR) X -ROH by further adding theproduct of the reaction of said alkyl tin with said aluminum halide at atemperature comprised between 20 and C.

References Cited UNITED STATES PATENTS 3,066,132 11/1962 Edmonds 260-9493,072,631 1/1963 Joyner 260---94.9 3,073,811 1/1963 Natta et al. 260-9373,202,617 8/1965 Enk et al. 252-429 3,210,334 10/1965 Carrick 26094.93,328,378 6/1967 Pierkarski et a1 260-94.9 3,424,737 1/ 1969 Delbouilleet al. 26094.9 3,006,910 10/1961 Pritchett et al. 260-949 3,116,27412/1963 Boehm et al. 260-949 FOREIGN PATENTS 860,407 2/1961 GreatBritain .26094.9E

944,371 12/ 1963 Great Britain 26094.9B 1,022,039 3/1966 Great Britain26094.9B

JOSEPH L. SCHOFER, Primary Examiner E. J. SMITH, Assistant Examiner U.S.Cl. X.R.

